Multinuclear NMR in polypeptide liquid crystals: Three fertile decades of methodological developments and analytical challenges

[Display omitted] •Progress of NMR in polypeptide-based media during three decades is reviewed.•Anisotropic NMR interactions (RCSA, RDC, RQC) depend on molecular orientational order.•Spectral enantiodiscriminations originate from the chirality of the aligned solvents.•Equations for anisotropic 1H, 2...

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Bibliographic Details
Published in:Progress in nuclear magnetic resonance spectroscopy 2020-02, Vol.116, p.85-154
Main Authors: Lesot, Philippe, Aroulanda, Christie, Berdagué, Philippe, Meddour, Abdelkrim, Merlet, Denis, Farjon, Jonathan, Giraud, Nicolas, Lafon, Olivier
Format: Article
Language:English
Subjects:
Analytical applications
Analytical chemistry
Anisotropic NMR
Chemical Sciences
or physical chemistry
Polypeptide oriented media
Spectral enantiodetection
Stereochemistry
Theoretical and
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Summary:[Display omitted] •Progress of NMR in polypeptide-based media during three decades is reviewed.•Anisotropic NMR interactions (RCSA, RDC, RQC) depend on molecular orientational order.•Spectral enantiodiscriminations originate from the chirality of the aligned solvents.•Equations for anisotropic 1H, 2H and 13C nD NMR are presented and discussed.•Applications include chirality studies, isotopic distribution and structural analysis. NMR spectroscopy of oriented samples makes accessible residual anisotropic intramolecular NMR interactions, such as chemical shift anisotropy (RCSA), dipolar coupling (RDC), and quadrupolar coupling (RQC), while preserving high spectral resolution. In addition, in a chiral aligned environment, enantiomers of chiral molecules or enantiopic elements of prochiral compounds adopt different average orientations on the NMR timescale, and hence produce distinct NMR spectra or signals. NMR spectroscopy in chiral aligned media is a powerful analytical tool, and notably provides unique information on (pro)chirality analysis, natural isotopic fractionation, stereochemistry, as well as molecular conformation and configuration. Significant progress has been made in this area over the three last decades, particularly using polypeptide-based chiral liquid crystals (CLCs) made of organic solutions of helically chiral polymers (as PBLG) in organic solvents. This review presents an overview of NMR in polymeric LCs. In particular, we describe the theoretical tools and the major NMR methods that have been developed and applied to study (pro)chiral molecules dissolved in such oriented solvents. We also discuss the representative applications illustrating the analytical potential of this original NMR tool. This overview article is dedicated to thirty years of original contributions to the development of NMR spectroscopy in polypeptide-based chiral liquid crystals.
ISSN:0079-6565
1873-3301
DOI:10.1016/j.pnmrs.2019.10.001